The aluminum precursor plays a crucial role in the Al₂O₃ ALD process. To date, trimethylaluminum (TMA) is one of the most widely used precursors in experimental and theoretical studies. However, its application at industrial scale can pose safety risks since it is pyrophoric and extremely reactive with water. Aluminum alkoxides offer a promising alternative, but have received far less attention. A combined theoretical and experimental investigation is carried out on the Al₂O₃ ALD process using aluminum triisopropoxide (ATIP) as a prototypical example of Al-alkoxide precursors. The experimental results pointed out that the thermal ALD process using ATIP and water has a maximal growth per cycle (GPC) of 1.8 Å/cycle at temperatures of 150 to 175 °C. On the basis of the in situ mass spectrometry analysis and DFT calculations, the formation of the alumina film mainly occurs during the water pulse by ligand exchange reactions between water and adsorbed precursors, while during the ATIP pulse only adsorption of ATIP and/or its dissociation occur. Design of heteroleptic precursors containing alkoxide group as basic ligand is challenging, but greatly promising for future industrial scale Al₂O₃ ALD.

Atomic layer deposition (ALD), a gas-phase thin film deposition technique based on repeated, self-terminating gas-solid reactions, has become the method of choice in semiconductor manufacturing and many other technological areas for depositing thin conformal inorganic material layers for various applications. ALD has been discovered and developed independently, at least twice, under different names: atomic layer epitaxy (ALE) and molecular layering. ALE, dating back to 1974 in Finland, has been commonly known as the origin of ALD, while work done since the 1960s in the Soviet Union under the name "molecular layering" (and sometimes other names) has remained much less known. The virtual project on the history of ALD (VPHA) is a volunteer-based effort with open participation, set up to make the early days of ALD more transparent. In VPHA, started in July 2013, the target is to list, read and comment on all early ALD academic and patent literature up to 1986. VPHA has resulted in two essays and several presentations at international conferences. This paper, based on a poster presentation at the 16th International Conference on Atomic Layer Deposition in Dublin, Ireland, 2016, presents a recommended reading list of early ALD publications, created collectively by the VPHA participants through voting. The list contains 22 publications from Finland, Japan, Soviet Union, United Kingdom, and United States. Up to now, a balanced overview regarding the early history of ALD has been missing; the current list is an attempt to remedy this deficiency.